On the origin of altered diastereomeric ratios for anionic versus neutral reaction conditions in the oxy-cope/ene reaction: An interplay of experiment and computational modeling

Chemistry - A European Journal

Volumn 16, Issue 47, 2010, Pages 14124-14130

  Hooper, James ^a   Sauer, Effiette L O ^a   Arns, Steve ^a   Woo, Tom K ^a   Barriault, Louis ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

carbanions; cascade reaction; decalin; ene reaction; isomerization; oxy Cope reaction

Indexed keywords

CARBANIONS; CASCADE REACTIONS; DECALIN; ENE REACTION; OXY-COPE REACTION;

ISOMERIZATION; ISOMERS; MOLECULAR DYNAMICS; OLEFINS; ORGANIC SOLVENTS; QUANTUM CHEMISTRY;

REACTION KINETICS;

ALKENE; ANION; ETHER DERIVATIVE;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; COMPUTER SIMULATION; MOLECULAR DYNAMICS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM; X RAY CRYSTALLOGRAPHY;

ALKENES; ANIONS; COMPUTER SIMULATION; CRYSTALLOGRAPHY, X-RAY; ETHERS; MAGNETIC RESONANCE SPECTROSCOPY; MODELS, MOLECULAR; MOLECULAR DYNAMICS SIMULATION; STEREOISOMERISM;

EID: 78650269234     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201001302     Document Type: Article

References (22)

1. E. L. O. Sauer, J. Hooper, T. Woo, L. Barriault, J. Am. Chem. Soc. 2007, 129, 2112.
2. S. Arns, L. Barriault, Chem. Commun. 2007, 2211
3. E. L. O. Sauer, L. Barriault, J. Am. Chem. Soc. 2004, 126, 8569
4. S. Arns, L. Barriault, J. Org. Chem. 2006, 71, 1809.
5. D. Gauvreau, L. Barriault, J. Org. Chem. 2005, 70, 8840.
6. S. Arns, I. Denissova, M.-E. Lebrun, C. M. Grisé, L. Barriault, J. Org. Chem. 2007, 72, 9314.
7. W. Kohn, L. A. Sham, Phys. Rev. A 1965, 10, 1133.
8. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785
9. A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
10. Jaguar 6.0, Schrodinger LLC, Portland, 2005.
11. Spartan 02, Wavefunction Inc., Irvine, 2002.
12. J. J. P. Stewart, Comput. Chem. 1989, 10, 209.
13. D. J. Tannor, B. Marten, R. Murphy, R. A. Friesner, D. Sitkoff, A. Nicholls, M. Ringnalda, W. A. Goddard III, B. Honig, J. Am. Chem. Soc. 1994, 116, 11875.
14. CPMD, Version 3.13.2, IBM Research Division and MPI für Festkörperforschung, Stuttgart, 2008.
15. J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.
16. N. Troullier, J. L. Martins, Phys. Rev. B 1991, 43, 1993
17. L. Kleinman, D. M. Bylander, Phys. Rev. Lett. 1982, 48, 1425.
18. The counterion was not included since the anionic species but could reasonably be assumed to increase the energy barrier fort he ring inversion.
19. A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev. 1988, 88, 899.
20. A. Rauk, J. D. Andose, W. G. Frick, R. Tang, K. Mislow, J. Am. Chem. Soc. 1971, 93, 6507
21. G. B. Ellison, P. C. Engelking, W. C. Lineberger, J. Am. Chem. Soc. 1978, 100, 2556
22. P. R. Peoples, J. B. Grutzner, J. Am. Chem. Soc. 1980, 102, 4709.